The reaction of elemental Se with 1,3‐dimethylimidazolium iodide in methanolic K2CO3 yields 1,3‐dimethyl‐2(3H)‐imidazoleselone for which three addition products, two with bromine and one with iodomethane, have been synthesized and for which X‐ray crystallographic analysis shows the structure to consist of a selenium‐substituted planar heterocyclic ring with bond distances and angles significantly different from those noted for the previously reported sulfur analog [1,3‐dimethyl‐2(3H)‐imidazolethione, dmit]. Crystal data: C5H8N2Se, space group C mcm, M = 175.03, a = 8.625(3), b = 11.447(6), c = 6.900(4) Å, V = 681.24 Å3, Z = 4, Dc = 1.707 g cm−3, D0 = 1.68 g cm−3, λ = 0.71073 Å (Mo‐Kα), μ = 5.35 mm−1, R = 0.034, and Rw = 0.031.

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